HYDROCARBONATED POLYMERS WITH TWO ALCOXYSILANE END GROUPS

Abstract

The invention relates to 1) a hydrocarbonated polymer comprising two alcoxysilane end groups of formula (1), and 2) a method for producing said polymer, an adhesive composition comprising said polymer and the use of said adhesive composition.

##STR00001##

Claims

1-15. (canceled)

16. A hydrocarbon polymer comprising two alkoxysilane end groups, said hydrocarbon polymer being of following formula (1): ##STR00042## wherein: F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—COO—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—OOC—NH—R″—SiR.sub.z(OR′).sub.3-z; or F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—CO—NH—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—NH—CO—NH—R″—SiR.sub.z(OR′).sub.3-z; or F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—CO—(CH.sub.2).sub.p2— and F.sub.2 is —(CH.sub.2).sub.q2—CONH—R″—SiR.sub.z(OR′).sub.3-z; wherein z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer equal to 1, 2 or 3; p2 and q2 are independently an integer equal to 0, 1, 2 or 3; the R and R′ groups are independently an alkyl group; the R″ group is an alkylene group comprising from 1 to 4 carbon atoms; and wherein: each carbon-carbon bond of the chain denoted is a double bond or a single bond, in accordance with the valency rules of organic chemistry; the R1, R2, R3, R4, R5, R6, R7 and R8 groups are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, it being possible for at least one of the R1 to R8 groups to form part of one and the same saturated or unsaturated ring or heterocycle with at least one other of the R1 to R8 groups, according to the valency rules of organic chemistry, and it being possible for at least one of the (R1,R2), (R3,R4), (R5,R6) and (R7,R8) pairs to be an oxo group; x and y are integers independently within a range extending from 0 to 5; the R14, R15, R16 and R17 groups are independently a hydrogen, a halogen atom, an alkyl group, an alkenyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, it being possible for at least one of the R14 to R17 groups to form part of one and the same saturated or unsaturated ring or heterocycle with at least one other of the R14 to R17 groups, according to the valency rules of organic chemistry; the R20 group is CH.sub.2, O, S, NR.sub.0 or C(═O), R.sub.0 being an alkyl or alkenyl group comprising from 1 to 22 carbon atoms; and n is an integer greater than or equal to 2 and m is an integer greater than or equal to 0, the molar ratio m:n being within a range from 0:1 to 0.5:1, n and m in addition being such that the number-average molar mass Mn of the hydrocarbon polymer of formula (1) is within a range from 400 to 50,000 g/mol, and the polydispersity (PDI) of the hydrocarbon polymer of formula (1) is within a range from 1.0 to 3.0.

17. The hydrocarbon polymer of claim 16, wherein x=y=1.

18. The hydrocarbon polymer of claim 16, wherein m is equal to 0, whereby the polymer is of the following formula (2): ##STR00043##

19. The hydrocarbon polymer of claim 16, wherein the polymer has the formula (1′): ##STR00044##

20. The hydrocarbon polymer of claim 16, wherein F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—COO—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—OOC—NH—R″—SiR.sub.z(OR′).sub.3-z, with p1=1 or q1=1.

21. The hydrocarbon polymer of claim 20, wherein R′ is a methyl, R″ is a —CH.sub.2— or —(CH.sub.2).sub.3— group, z=0, p1=1 and q1=1.

22. The hydrocarbon polymer of claim 16, wherein F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—CO—NH—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—NH—CO—NH—R″—SiR.sub.z(OR′).sub.3-z, with p1=1 or q1=1.

23. The hydrocarbon polymer of claim 22, wherein R′ is a methyl, R″ is a —CH.sub.2— or —(CH.sub.2).sub.3— group, z=0, p1=1 and q1=1.

24. The hydrocarbon polymer of claim 16, wherein F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—CO—(CH.sub.2).sub.p2— and F.sub.2 is —(CH.sub.2).sub.q2—CONH—R″—SiR.sub.z(OR′).sub.3-z, with p2=0 or q2=0.

25. The hydrocarbon polymer of claim 24, wherein R′ is a methyl, R″ is a —CH.sub.2— or —(CH.sub.2).sub.3— group, z=0, p2=0 and q2=0.

26. A process for the preparation of the hydrocarbon polymer of claim 16, said process comprising at least one stage of ring-opening metathesis polymerization, in the presence of: at least one metathesis catalyst, at least one difunctional alkoxysilane chain transfer agent (CTA) of the following formula (C): ##STR00045## in which the bond is a bond geometrically oriented on one side or the other, with respect to the double bond (cis or trans); F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—COO—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—OOC—NH—R″—SiR.sub.z(OR′).sub.3-z; or F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—CO—NH—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—NH—CO—NH—R″—SiR.sub.z(OR′).sub.3-z; or F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—CO—(CH.sub.2).sub.p2— and F.sub.2 is —(CH.sub.2).sub.q2—CO—NH—R″—SiR.sub.z(OR′).sub.3-z; wherein z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer equal to 1, 2 or 3; p2 and q2 are independently an integer equal to 0, 1, 2 or 3; the R and R′ groups are independently an alkyl group; the R″ group is an alkylene group; at least one compound of the following formula (A): ##STR00046## wherein: the R1, R2, R3, R4, R5, R6, R7 and R8 groups are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, it being possible for at least one of the R1 to R8 groups to form part of one and the same saturated or unsaturated ring or heterocycle with at least one other of the R1 to R8 groups, according to the valency rules of organic chemistry, and it being possible for at least one of the (R1,R2), (R3,R4), (R5,R6) and (R7,R8) pairs to be an oxo group; x and y are integers independently within a range extending from 0 to 5; and optionally at least one compound of formula (B): ##STR00047## wherein: the R14, R15, R16 and R17 groups are independently a hydrogen, a halogen atom, an alkyl group, an alkenyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, it being possible for at least one of the R14 to R17 groups to form part of one and the same saturated or unsaturated ring or heterocycle with at least one other of the R14 to R17 groups, according to the valency rules of organic chemistry; and the R20 group is CH.sub.2, O, S, NR.sub.0 or C(═O), R.sub.0 being an alkyl group; for a reaction time ranging from 2 to 24 hours and at a temperature within a range from 20 to 60° C.

27. The process of claim 26, wherein the molar ratio of the CTA to the compound of formula (A), or to the sum of the compounds of formulae (A) and (B) if the compound of formula (B) is present, is within a range from 0.01 to 0.10.

28. The process of claim 26, wherein the CTA is selected from the group consisting of: ##STR00048##

29. An adhesive composition comprising the polymer of claim 16 and from 0.01 to 3% by weight of at least one crosslinking catalyst, with respect to the weight of the adhesive composition.

30. A process for adhesive bonding by assembling two substrates, comprising: coating the adhesive composition of claim 29, in the liquid form, onto a surface of at least one of the two substrates; and bringing the two substrates into contact along their faying surfaces.

Description

EXAMPLES

[0135] The synthesis reactions of the examples were carried out in two or three stages, with a stage of synthesis of the cycloolefin, a stage of synthesis of the transfer agent (CTA) of formula (C) and a stage of ring-opening metathesis polymerization of cycloolefin of formula (A) and optionally of compound of formula (B) in the presence of a Grubbs catalyst and of the transfer agent.

[0136] The general scheme 1 of the polymerization reactions carried out in examples 1 to 8 is given below and will be clarified on an individual basis in the detailed examples.

##STR00024##

In this scheme 1:

[0137] DCM means dichloromethane

[0138] the bond is a bond geometrically oriented on one side or the other, with respect to the double bond (cis or trans); CTA is the chain transfer agent of formula (C); the cycloolefins are of formulae (A) and (B),

[0139] G2 is the metathesis catalyst of formula (9):

##STR00025##

in which Ph is phenyl and Cy is cyclohexyl;

[0140] the F.sub.1 and F.sub.2 groups are symmetrical and correspond respectively to the —CH.sub.2—OOC—NH—(CH.sub.2).sub.3—Si(OCH.sub.3).sub.3 group (case where the CTA is a γ-dicarbamate), to the —CH.sub.2—NH—CO—NH—(CH.sub.2).sub.3—Si(OCH.sub.3).sub.3 group (case where the CTA is a γ-diurea) and to the —CO—NH—(CH.sub.2).sub.3—Si(OCH.sub.3).sub.3 group (case where the CTA is a γ-diamide);

[0141] n is the number of moles of cycloolefins of formula (A);

[0142] m is the number of moles of cycloolefins of formula (B);

[0143] x is the number of moles of CTA of formula (C).

[0144] The number of monomer units in the polymer is equal to n+m.

[0145] In each of examples 1 to 8 described below using scheme 1, the reaction lasts 24 h at a temperature of 40° C.

[0146] All the polymerizations were carried out similarly. The only differences lie in the nature and the initial concentration of the chain transfer agent(s) (CTA). The γ-dicarbamate (CTA.sup.1), the γ-diurea (CTA.sup.2) and the γ-diamide (CTA.sup.3), illustrating the invention, which are used in examples 1 to 8, have the following respective formulae:

##STR00026##

(which corresponds to the case where F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—COO—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—OOC—NH—R″—SiR.sub.z(OR′).sub.3, with R′=methyl, R″═—(CH.sub.2).sub.3—, z=0, p1=1 and q1=1);

##STR00027##

(which corresponds to the case where F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—CO—NH—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—NH—CO—NH—R″—SiR.sub.z(OR′).sub.3, with R′=methyl, R″═—(CH.sub.2).sub.3—, z=0, p1=1 and q1=1);

##STR00028##

(which corresponds to the case where F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—NH—CO—(CH.sub.2).sub.p2— and F.sub.2 is —(CH.sub.2).sub.q2—CO—NH—R″—SiR.sub.z(OR′).sub.3, with R′=methyl, R″═—(CH.sub.2).sub.3—, z=0, p2=0 and q2=0).

[0147] Two reaction possibilities exist, according to whether the cycloolefin of formula (A) is used alone (examples 1 to 6) or according to whether the cycloolefins of formulae (A) and (B) are used as a mixture (examples 7 and 8).

Examples 1 to 6: Polymerization of the Cycloolefins of Formula (A)

[0148] ##STR00029##

[0149] The polymerization process described below corresponds to examples 1 to 4 (the results of which are shown in table 1 below), to example 5 (cf table 2) and to example 6 (cf table 3).

[0150] The cycloolefins of formula (A) used in these examples are as follows:

##STR00030##

[0151] The cyclooctene (COE) and the 5,6-epoxycyclooctene (5-epoxyCOE) were commercial products from Sigma-Aldrich.

[0152] The 5-oxocyclooctene (5-O═COE) and the 5-n-hexyl-cyclooctene (5-hexyl-COE) were synthesized from 5,6-epoxycyclooctene (5-epoxy-COE) according to the route shown in the following reaction scheme 2:

##STR00031##

[0153] The 5-oxocyclooctene (5-O═COE, referenced 2 in the scheme above) was synthesized according to the procedure shown in the publication of A. Diallo et al., Polymer Chemistry, Vol. 5, Issue 7, 7 Apr. 2014, pp. 2583-2591 (which referred to Hillmyer et al., Macromolecules, 1995, 28, 6311-6316).

[0154] The 5-hexylcyclooctene (5-hexyl-COE, referenced 5 in the scheme above) was synthesized according to the procedure shown in the publication of A. Diallo et al., Polymer Chemistry, mentioned above (which referred to Kobayashi et al., J. Am. Chem. Soc., 2011, 133, pp. 5794-5797).

[0155] The starting materials, reactants and solvents used during these syntheses were commercial products from Sigma-Aldrich.

[0156] A cycloolefin of formula (A) described above (10.8 mmol) and dry CH.sub.2Cl.sub.2 (5 ml) were placed in a 100 ml round-bottomed flask in which was also placed a Teflon®-coated magnetic stirring bar. The round-bottomed flask and its contents were subsequently placed under argon. The compound of formula CTA.sup.1 (0.54 mmol) was then introduced using a syringe into the round-bottomed flask. The round-bottomed flask was then immersed in an oil bath at 40° C. and then the catalyst G2 (5.4 μmol) in solution in CH.sub.2Cl.sub.2 (2 ml) was immediately added using a hollow needle. The reaction mixture then became very viscous in the space of two minutes. The viscosity subsequently slowly decreased over the following 10 minutes. After 24 h, counting from the addition of the catalyst, the product present in the round-bottomed flask was extracted after the solvent was concentrated under vacuum. A product was then recovered after precipitating from methanol, filtering and drying at 20° C. under vacuum (Yield of greater than 90% for each of examples 1 to 6). The .sup.1H/.sup.13C NMR analysis made it possible to demonstrate that the product was indeed a polymer having the expected formula.

[0157] All the polymers prepared in the examples were recovered as a solid powder or as a liquid, depending on the nature of the cycloolefin, which is colorless, easily soluble in chloroform and insoluble in methanol.

[0158] The different tests of examples 1 to 6 are summarized in tables 1, 2 and 3 described in detail below.

TABLE-US-00001 TABLE 1 Conversion Mn.sub.SEC Test No. [A]/[CTA.sup.1]/[Ru] (mol/mol) A (%) (g/mol) PDI 1 2 000/100/1 4 600 1.53 2 2 000/100/1 100 5 200 1.47 3 2 000/100/1 100 4 800 1.50 4 2 000/100/1 100 5 000 1.51 where CTA.sup.1 = γ-dicarbamate

TABLE-US-00002 TABLE 2 Conversion Mn.sub.SEC Test No. [A]/[CTA.sup.2]/[Ru] (mol/mol) A (%) (g/mol) PDI 5 2 000/100/1 100 4 900 1.49 where CTA.sup.2 = γ-diurea

TABLE-US-00003 TABLE 3 Conversion Mn.sub.SEC Test No. [A]/[CTA.sup.3]/[Ru] (mol/mol) A (%) (g/mol) PDI 6 2 000/100/1 100 5 300 1.52 where CTA.sup.3 = γ-diamide

Example 1: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from Cyclooctene (COE) and CTA.SUP.1

[0159] The reaction was carried out according to the following scheme 3:

##STR00032##

The polymer obtained was solid at ambient temperature.

[0160] The NMR analyses of the polymer obtained for this test gave the following values, which have confirmed the structure of the polymer:

[0161] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeat unit 1.29 (8H*n), 1.96 (4H*n), 5.37 (2H*n), end group=0.64 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.61 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.16 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3), 4.48 (4H, t, —CO—O—CH.sub.2—CH═), 5.73 (2H, m, —CH═CH—CH.sub.2—O—CO—), 5.77 (2H, m, —CH═CH—CH.sub.2—O—CO—).

[0162] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeat unit 29.17, 29.54, 29.78, 32.37, 33.10, 130.48, end group=6.28 (—CH.sub.2—CH.sub.2—Si—), 23.17 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 43.34 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.77 (—Si—O—CH.sub.3), 65.57 (—CO—O—CH.sub.2—CH═), 124.41 (CH═CH—CH.sub.2—O—CO—), 136.05 (—CH═CH—CH.sub.2—O—CO—), 156.50 (—O—CO—).

Example 2: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from Cyclooctene Monoepoxide (5-EpoxyCOE) and CTA.SUP.1

[0163] The reaction was carried out according to the following scheme 4:

##STR00033##

The polymer obtained was liquid at ambient temperature.

[0164] The NMR analyses of the polymer obtained for this test gave the following values, which have confirmed the structure of the polymer:

[0165] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeat unit 1.29 (4H*n), 1.96 (4H*n), 2.72 (2H*n), 5.37 (2H*n), end group=0.64 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.61 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.16 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3), 4.48 (4H, t, —CO—O—CH.sub.2—CH═), 5.73 (2H, m, —CH═CH—CH.sub.2—O—CO—), 5.77 (2H, m, —CH═CH—CH.sub.2—O—CO—).

[0166] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeat unit 29.17, 29.54, 29.78, 32.37, 33.10, 56.72, 130.48, end group=6.28 (—CH.sub.2—CH.sub.2—Si—), 23.17 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 43.34 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.77 (—Si—O—CH.sub.3), 65.57 (—CO—O—CH.sub.2—CH═), 124.41 (CH═CH—CH.sub.2—O—CO—), 136.05 (—CH═CH—CH.sub.2—O—CO—), 156.50 (—O—CO—).

Example 3: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from 5-oxocyclooctene (5-O═COE) and CTA.SUP.1

[0167] The reaction was carried out according to the following scheme 5:

##STR00034##

The polymer obtained was solid at ambient temperature.

[0168] The NMR analyses of the polymer obtained for this test gave the following values, which have confirmed the structure of the polymer:

[0169] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeat unit 1.56 (2H*n), 1.91 (2H*n), 2.17-2.53 (6H*n), end group=0.64 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.61 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.16 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3), 4.48 (4H, t, —CO—O—CH.sub.2—CH═), 5.73 (2H, m, —CH═CH—CH.sub.2—O—CO—), 5.77 (2H, m, —CH═CH—CH.sub.2—O—CO—).

[0170] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeat unit 21.51, 23.31, 26.53, 31.82, 42.17, 130.48, end group=6.28 (—CH.sub.2—CH.sub.2—Si—), 23.17 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 43.34 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.77 (—Si—O—CH.sub.3), 65.57 (—CO—O—CH.sub.2—CH═), 124.41 (CH═CH—CH.sub.2—O—CO—), 136.05 (—CH═CH—CH.sub.2—O—CO—), 156.50 (—O—CO—).

Example 4: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from 5-hexylcyclooctene (5-Hexyl-COE) and CTA.SUP.1

[0171] The reaction was carried out according to the following scheme 6:

##STR00035##

The polymer obtained was liquid at ambient temperature.

[0172] The NMR analyses of the polymer obtained for this test gave the following values, which have confirmed the structure of the polymer:

[0173] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeat unit 0.83 (3H*n), 1.19 (2H*n), 1.27 (8H*n), 1.75 (2H*n), 1.96 (4H*n), 5.37 (2H*n), end group=0.64 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.61 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.16 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3), 4.48 (4H, t, —CO—O—CH.sub.2—CH═), 5.73 (2H, m, —CH═CH—CH.sub.2—O—CO—), 5.77 (2H, m, —CH═CH—CH.sub.2—O—CO—).

[0174] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeat unit 14.1, 22.7, 27.4, 29.6, 31.8, 32.37, 33.10, 33.8, 40.65, 130.48, end group=6.28 (—CH.sub.2—CH.sub.2—Si—), 23.17 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 43.34 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.77 (—Si—O—CH.sub.3), 65.57 (—CO—O—CH.sub.2—CH═), 124.41 (CH═CH—CH.sub.2—O—CO—), 136.05 (—CH═CH—CH.sub.2—O—CO—), 156.50 (—O—CO—).

Example 5: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from Cyclooctene (COE) and CTA.SUP.2

[0175] The reaction was carried out according to the following scheme 7:

##STR00036##

The polymer obtained was solid at ambient temperature.

[0176] The NMR analyses of the polymer obtained for this test gave the following values, which have confirmed the structure of the polymer:

[0177] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeat unit 1.29 (8H*n), 1.96 (4H*n), 5.37 (2H*n), end group=0.64 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.61 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.21 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3), 3.83 (4H, t, —CO—NH—CH.sub.2—CH═).

[0178] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeat unit 29.17, 29.54, 29.78, 32.37, 33.10, 130.48, end group=6.28 (—CH.sub.2—CH.sub.2—Si—), 23.17 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 43.34 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.77 (—Si—O—CH.sub.3), 52.57 (—CH═CH—CH.sub.2—NH—CO—), 124.41 (—CH═CH—CH.sub.2—NH—CO—), 136.05 (—CH═CH—CH.sub.2—NH—CO—), 157.45 (—O—CO—).

Example 6: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from Cyclooctene (COE) and CTA.SUP.3

[0179] The reaction was carried out according to the following scheme 8:

##STR00037##

The polymer obtained was solid at ambient temperature.

[0180] The NMR analyses of the polymer obtained for this test gave the following values, which have confirmed the structure of the polymer:

[0181] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeat unit 1.29 (8H*n), 1.96 (4H*n), 5.37 (2H*n), end group=0.64 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.61 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.18 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3), 6.26 (2H, m, —CH═CH— CO—), 6.62 (2H, m, —CH═CH—CO—).

[0182] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeat unit 29.17, 29.54, 29.78, 32.37, 33.10, 130.48, end group=6.28 (—CH.sub.2—CH.sub.2—Si—), 23.17 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 43.34 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.77 (—Si—O—CH.sub.3), 126.20 (CH═CH—CO—NH), 148.7 (—CH═CH—CO—NH), 167.18 (—CO—NH).

Examples 7 and 8: Polymerization of a Mixture of Cycloolefins of Formulae (A) and (B)

[0183] ##STR00038##

[0184] The polymerization process described below corresponds to examples 7 and 8, the results of which are shown in tables 4 and 5 below. The cycloolefins of formulae (A) and (B) used in examples 7 and 8 are respectively as follows:

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[0185] The cyclooctene (COE) with a purity of greater than 95% and the norbornene (NBN) with a purity of greater than 99% were commercial products from Sigma-Aldrich. They were distilled beforehand over CaH.sub.2.

[0186] The starting materials, reactants and solvents used during these syntheses were commercial products from Sigma-Aldrich.

[0187] The cycloolefins of formulae (A) and (B), respectively COE (5.4 mmol) and NBN (5.4 mmol) described above, and dry CH.sub.2Cl.sub.2 (5 ml) were placed in a 100 ml round-bottomed flask in which was also placed a Teflon®-coated magnetic stirring bar. The round-bottomed flask and its contents were subsequently placed under argon. The compound of formula CTA.sup.1 (for example 7) or CTA.sup.3 (for example 8) (0.54 mmol) was then introduced into the round-bottomed flask using a syringe. The round-bottomed flask was then immersed in an oil bath at 40° C. and then the catalyst G2 (5.4 μmol) in solution in CH.sub.2Cl.sub.2 (2 ml) was immediately added using a hollow needle. The reaction mixture then became very viscous in two minutes. The viscosity subsequently slowly decreased over the following 10 minutes. After 24 hours, counting from the addition of the catalyst, the product present in the round-bottomed flask was extracted after the solvent was concentrated under vacuum. A product was then recovered after precipitating from methanol, filtering and drying at 20° C. under vacuum (Yield 94% in this case). The .sup.1H/.sup.13C NMR analysis made it possible to demonstrate that the product was indeed a polymer having the expected formula.

[0188] All the polymers prepared in the examples were recovered as a solid powder or as a liquid, depending on the NBN/COE molar ratio, which is colorless, easily soluble in chloroform and insoluble in methanol.

[0189] The different tests of examples 7 and 8 are summarized in tables 4 and 5 and described in detail below.

TABLE-US-00004 TABLE 4 Test Conversion Mn.sub.SEC No. [A]/[B]/[CTA.sup.1]/[Ru] (mol/mol) (%) (g/mol) PDI 7 1 000/1 000/100/1 100 4900 1.60 where CTA.sup.1 = β-dicarbamate

TABLE-US-00005 TABLE 5 Test Conversion Mn.sub.SEC No. [A]/[B]/[CTA.sup.3]/[Ru] (mol/mol) (%) (g/mol) PDI 8 1 000/1 000/100/1 100 4800 1.58 where CTA.sup.3 = β-diamide

Example 7: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from Cyclooctene (COE), Norbornene (NBN) and CTA.SUP.1

[0190] The reaction was carried out according to the following scheme 9, in a molar ratio m:n equal to 0.3:1.0:

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The polymer obtained was liquid at ambient temperature.

[0191] The NMR analyses of the polymer obtained for this test gave the following values, which have confirmed the structure of the polymer:

[0192] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeat unit trans: 1.23 (12H*n), 1.72-1.89 (6H*n), 2.37 (2H*n trans), 5.31 (2H*n trans), cis: 1.23 (12H*n), 1.72-1.89 (6H*n), 2.72 (2H*n cis), 5.13 (2H*n cis), end group=0.64 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.61 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.16 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3), 4.48 (2H, t, —CO—O—CH.sub.2—CH═), 5.73 (2H, m, —CH═CH—CH.sub.2—O—CO—), 5.77 (2H, m, —CH═CH—CH.sub.2—O—CO—).

[0193] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeat unit: 29.17, 29.54, 29.78, 32.37, 33.10, 38.02, 38.67, 41.35, 42.77, 43.13, 43.52, 130.35, 134.89, end group=6.28 (—CH.sub.2—CH.sub.2—Si—), 23.17 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 43.34 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.77 (—Si—O—CH.sub.3), 65.57 (—CO—O—CH.sub.2—CH═), 124.41 (CH═CH—CH.sub.2—O—CO—), 136.05 (—CH═CH—CH.sub.2—O—CO—), 156.50 (—O—CO—).

Example 8: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from Cyclooctene (COE), Norbornene (NBN) and CTA.SUP.3

[0194] The reaction was carried out according to the following scheme 10, in a molar ratio m:n equal to 0.3:1.0:

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The polymer obtained was liquid at ambient temperature.

[0195] The NMR analyses of the polymer obtained for this test gave the following values, which have confirmed the structure of the polymer:

[0196] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): δ (ppm) repeat unit trans: 1.23 (12H*n), 1.72-1.89 (6H*n), 2.37 (2H*n trans), 5.31 (2H*n trans), cis: 1.23 (12H*n), 1.72-1.89 (6H*n), 2.72 (2H*n cis), 5.13 (2H*n cis), end group=0.64 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.61 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.18 (4H, m, —NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3), 6.26 (2H, m, —CH═CH— CO—), 6.62 (2H, m, —CH═CH—CO—).

[0197] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): δ (ppm) repeat unit: 29.17, 29.54, 29.78, 32.37, 33.10, 38.02, 38.67, 41.35, 42.77, 43.13, 43.52, 130.35, 134.89, end group=6.28 (—CH.sub.2—CH.sub.2—Si—), 23.17 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 43.34 (—NH—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.77 (—Si—O—CH.sub.3), 126.20 (CH═CH—CO—NH), 148.7 (—CH═CH— CO—NH), 167.18 (—CO—NH).

Example 9: Preparation of an Adhesive Composition from a Polymer Comprising Two Alkoxysilane End Groups

[0198] 8 adhesive compositions, each comprising 0.2% by weight of a crosslinking catalyst consisting of dioctyltin dineodecanoate (product Tib kat 223 from Tib Chemicals) and a polymer according to the invention obtained in examples 1 to 8, were prepared by simple mixing.

[0199] Each mixture thus obtained was left under reduced stirring (20 mbar, i.e. 2000 Pa) for 15 minutes, before the composition thus obtained is packaged in an aluminum cartridge.

[0200] The measurement of the breaking strength and of the elongation at break by a tensile test was carried out, for each of the 8 adhesive compositions, according to the protocol described below.

[0201] The principle of the measurement consists in drawing, in a tensile testing device, the moving jaw of which moves at a constant rate equal to 100 mm/min, a standard test specimen consisting of the crosslinked adhesive composition and in recording, at the moment when breaking of the test specimen occurs, the tensile stress applied (in MPa) and also the elongation of the test specimen (in %).

[0202] The standard test specimen has the shape of a dumbbell, as illustrated in the international standard ISO 37. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 μm.

[0203] In order to prepare the dumbbell, the composition, packaged as described above, was heated to 100° C. and then the amount necessary to form, on an A4 sheet of silicone-treated paper, a film having a thickness of 300 μm is extruded over this sheet, which film was left at 23° C. and 50% relative humidity for 7 days for crosslinking. The dumbbell is then obtained by simple cutting out from the crosslinked film.

[0204] The dumbbell of each of the 8 adhesive compositions tested then exhibits an ultimate strength of greater than 0.7 MPa with an elongation at break of greater than 200%.

[0205] Each adhesive composition was subsequently subjected to tests of adhesive bonding of two strips of wood (each with a size of 20 mm×20 mm×2 mm) in order to result, after crosslinking at 23° C. for seven days, in a breaking force of greater than 2 MPa in adhesive failure.